DE1568693A1 - UV-absorbing, light-stable compounds - Google Patents

Description

J. R. GEIGY A. G. BASEL 21

Dr. F. Zumsiein - Dr. E. Asjmann 2 219 * Dr. R. Koenigsberger Dipl. Phys. R. Hollbauer Patent attorney Mönchen 2, Bräuhaussfrafc «4 / J ||

UV-absorbing, light-stable compounds

The present invention relates to new UV-absorbing, light-stable compounds, their use for stabilizing light-sensitive organic material, and for manufacture of light filters, furthermore as an industrial product, which with their help improved in its light resistance organic material and light filters containing these UV-absorbing compounds, as well as methods of manufacture this new UV absorber.

It is known that certain methylene cyanoacetic acid and methylenemalodinitrile derivatives of the general formulas

Aryl CN - Aryl GN

C = C and C = C

yS \ / ■ \

Z COOAlkyl Z Ρ, Ν ... ^.

in which Z is hydrogen, an alkyl or aryl radical, absorb UV light. Of these connections have become in practice the two representatives α-carbethoxy and α-cyano-ßpheriyl-cinnamonitrile Tried and tested especially in nitrocellulose as a UV filter and light protection agent. Most of the others Representatives of this body class have either because of a lack of

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Lightfastness or insufficient light absorption is of no practical importance.

In addition to light fastness and absorption, the sublimation fastness of a light stabilizer also plays an increasing role Mass plays an essential role. At the high processing temperatures to which the thermoplastic plastics masses are exposed in today's machines built for high throughput, a considerable amount of the previously known ones sublimes Light stabilizers of the cinnamonitrile series from the thermoplastic mass away. This not only leads to a loss of light stabilizer and a reduction in the light stability of the processed Plastic, but in some cases also to contamination of the equipment, e.g. the injection molds, or too partial clogging of spinnerets. This disadvantage ο can is also unfavorable to aspect and even strength / ^ reshaped Impact plastics. The ones incorporated through volatility Light stabilizers caused disruptions in the production process are directly dependent on the amount of precipitated Sublimate; The relatively high volatility of the light stabilizers therefore means frequent interruptions in the production process and frequent cleaning the equipment and removal of the rejects.

It has now been found that the disadvantages outlined can largely be remedied if one is used as a light stabilizer the new bis-methylenemalonic acid compounds of the formula I. used,

BATH ORIGINAL

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n-1

dig is characterized by its low intrinsic color, its good lightfastness, its low sensitivity to alkali and heavy metals and its high Light absorption paired with excellent sublimation fastness mark *

In the general formula I and the formulas below mean

independently of one another the groups -COR ₁ or -CN, where R _{1 is} the group

^{and X} 2 *

-OR ₂ , -NHR ₂ , -

and -N

represents, v> rin the substituents R ₀ , R ^ and, R- do not have any of the atomic sequences -0-C-0-, -KCO- ₅ -NCS-, -C = CO- uni -C ^ CN-.

In these groups:

R «an optionally substituted alkyl group _5, preferably a ^ an unsubstituted alkyl group having 1 to 22 carbon atoms, such as methyl, ethyl, propyl, butyl, isobutyl, Cctyl, 2-ethylhexyl, Dodecyl or octadecyl group,

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BATH ORIGINAL

b) an oxaalkyl group with 3 to 21 carbon atoms,

for example a mono-oxaalkyl group, like the 2-methoxyethyl, 2-butoxyethyl, 2-decyloxyethyl or 4-methoxybutyl group, or a dioxa-alkyl group with 5 to 23 carbon atoms, such as the 2- (2 ~ iso-propoxyethoxy) ethyl group or the 4- (4-methoxybutoxy) -

butyl group ·;
♦

c) a hydroxyalkyl group with 2 to 12 carbon atoms,

. For example, the 2-hydroxyethyl, 2- or • 3-hydroxypropyl or 4-hydroxybutyl group,

d) a hydroxyoxaalkyl group with A to 12 carbon atoms,

for example a hydroxymono-oxa-alkyl-. group, such as the 2- (2-hydroxyethoxy) ethyl or propyl group or a hydroxydioxaalkyl group having 6 to 14 carbon atoms, such as the 2- [2- (2-hydroxyethoxy) ethoxy] ethyl or propyl group;

an optionally substituted alkenyl group, preferably

an unsubstituted alkenyl group with 3 to 18 carbon atoms, for example the allyl,

Methallyl-, ^ -undecylenyl- or

Λ 9

* - * -Octadecylenyl group;

an optionally substituted cycloalkyl group, preferably

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a hydrocarbon group, the one

5-membered ring and a total of 5 to 12 carbon atoms, such as the cyclopentyl or 2-methylcyclopentyl group, or one 6-membered ring with a total of 6 to 12 carbon atoms, such as the cyclohexyl or 4-butylcyclohexyl group;

an optionally substituted aralkyl group, preferably a hydrocarbon group of 7-19 C atoms, which has an optionally alkyl-substituted phenyl radical, for example the benzyl, α- and ß-phenyl-. ethyl-, o-methylbenzyl-, p-methylbenzyl-

or p-octylbenzyl group; an optionally substituted monooxa (aralkyl group), preferably with 8 to 24 carbon atoms and with one optionally alkoxy-substituted phenyl or alkyl-substituted phenoxy radical, for example the p-methoxybenzyl, p-butoxybenzyl, 2-phenoxyethyl, 2-benzyloxyethyl or 2- (p-dodecylphenoxy) ethyl group, or

an optionally substituted, in particular monocyclic aryl

f group, preferably "· '

an aryl hydrocarbon group of 6 to 20, or monooxa (alkylaryl) hydrocarbon group with 7 to 20 carbon atoms and especially one optionally by alkyl or Alkoxygrupp.en substituted phenylring,

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for example the phenyl,: "- ouer p-Xethylphenyl-, p-c.ButylpJr.ür.yl- » p-t.Octylphenyl-, p-t.Dodecylpr.er.yl-, the o- or p-xerhoxy or arhoxyphenyl or the rn-dodecyloxyphenyl group.

means the same as ^ j but preferably an unsubstituted alkyl group z.iz 1 to 22 carbon atoms, v / ie the methyl, ethyl, propyl, butyl, iso-3utyl _} octyl -, 2-ethylhexyl, Z / odecyl or C ^ ctadecyl group. . ,

means

an alkylene group which is preferably 4 to £ C atoms to the nitrogen: "is bound, for example a Tetra, A.ntaier Hexa.r.etnyler.gruppe; or

^BATH

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a monooxaalkylene or monothiaalkylene group with preferably A to 8 carbon atoms, for example

the groups -GH ₂ CH ₂ -O-GH ₂ GH ₂ -, -CH ₂ -CH-O-CH ₂ CH ₂ -

CH ₃

-CH ₂ -CH-O-CH ₂ CH ₂ -, -CH ₂ -CH ₂ -S-CH ₂ -CH ₂ - or CH ₂ CH ₂ CH ₂ CH ₃

-CH ₀ -CH-S-CH-GH ₀ -,
CH ₃ CH ₃

which groups together with the nitrogen atom form a 5 to 7 membered saturated azaheterocycle form.

- Furthermore I mean in the general formula and the following formulas:

Y and Y 'each have a divalent radical of the formula -NHCO-,

-NHSO ₂ -, -NHCOO-, which is bonded to ring A or B with the nitrogen, but preferably -0-,

R, - and Rc ¹ particularly denote an optionally substituted aryl group

an aryl hydrocarbon group with 6 to 18 carbon atoms and preferably an alkyl or alkoxy substituted phenyl radical, for example the phenyl, p-methylphenyl, p-t, butylphenyl or p-octylphenyl, p-methoxyphenyl or o-dodecyloxyphenyl group5 and

when all X are exclusively -COR ^ groups, R ₅ and R _{5 are} ¹

in addition to the aryl group also nooh, namely, preferably Hj

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when at least 2 of the X are cyano groups, R ₅ and Rc are ¹

in addition to the aryl group, also>

an optionally substituted alkyl group, preferably a substituted lower alkyl group, for example the methyl, ethyl, iso-propyl or butyl group; or

an optionally substituted aralkyl group, preferably an aralkyl hydrocarbon group with 7 to 19 carbon atoms and 6-membered mononuclear carbocyclic! Aryl part, for example the benzyl or 2-phenethyl group «
R, - means

an alkylene group with preferably 2 to 12 carbon atoms, for example the 1,2-ethylene, 1,2-propylene, Trimethylene, tetramethylene, pentamethylene, octamethylene, dodecamethylene, 2,2,5-trimethylhexamethylene or 2,5-diethylhexamethylene group;

a monooxa or monothiaalkylene group with preferably 4 to 12 carbon atoms, for example the groups -CH ₂ CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₂ Ch ₂ CH ₂ - or -CH ₂ CH ₂ CH ₂ -S-CH ₂ CH ₂ CH ₂ -;

a dioxa or dithiaalkylene group with advantageous 6 to 14 carbon atoms, for example the groups

-CH ₂ CH ₂ -O-CH ₂ Ch ₂ -O-CH ₂ CH ₂ -, -CH ₂ -Ch-O-CH ₂ CH ₂ -O-CH-CH _2. ,

CH ₃ CH ₃

- oier

-CH ₉ CH ₉ -S-CH-CH-S-CH ₉ Ch ₀ -;
cc ,, dd

CH ₃ CH ₃

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a cycloalkylene group with preferably 4 to 12 carbon atoms, for example the groups

¹ CH -CH ^CH 3 _Nc / ^CH 3

-CH ₀ -CH OH-CH ₀ , -CH 'CH- or

CH ₃ CH ₃

an aralkylene group, preferably an aralkylene hydrocarbon group with 8 to 22 carbon atoms, for example the groups

■ ^CH 2 ~ \ / ~ ^CH 2 ~ '-CH ₂ - ^ Jy-CH ₂ CH ₂ CH ₂ CH ₂ - or

2 ~ \ / ~ ^CH 2

CH ₃ CH ₃
^ -C-CH ₉ -C-CHo J or

-CH ₂ CH ₃ CH ₃

a monooxaaralkylene group, especially a monooxaaralkylene hydrocarbon group with 9 to 21 carbon atoms, the aryl part being the aralkylene and monooxaaralkylene groups, preferably one which is optionally alkyl- or alkoxy-substituted Is phenylene radical, for example the groups

BAD ORiGiNAt

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—Ν / s

^ VOGH ₉ GIL-, -Oil

and

if Y or Y ^{1 is} a nitrogen-containing group, i.e., -MHCO-, -NHSO ₂ - or -WHCOO-, also a phenylene group

and also 2 or more present in Rg or bound to Rg Heteroatoms separated by at least two carbon atoms each and bound to Rg, this with the Oxygen atoms connecting benzene rings A and B are bonded to saturated carbon atoms of Rg} η means 2 or for the Faii that Y is oxygen also 1.

The compounds of the formula (I) preferably contain

! 1 1

the groups X-,, X ₂ , X,, Xp, R ₅ , R ₅ and Rg together do not have more than 86 carbon atoms.

In the above terms, an oxa or thia hydrocarbon radical means a hydrocarbon radical in which a non-terminal ie. a middle 3H ₂ group is replaced by an oxygen or sulfur atom. The groupings are examples

-CH ₀ -CH ₀ -O-CH ₀ -CH, and -CH “-C-C3 called.

The 1,4-phenylene rings A and B can be chemically inert and non-coloring substituents be substituted, preferably

_o wisely, however, they are unsubstituted in positions 2, 3, 5 and 6

to or in a maximum of 2 of these positions by halogen, both

- »for example fluorine, chlorine or bromine, lower alkyl groups, for example methyl, ethyl or butyl groups, or alkoxy groups with 1 to 8 carbon atoms, for example methoxy, ethoxy or» j t - -

Octyloxy groups substituted. ß / UD oFUGINAl

The new bismethylene malonic acid derivatives can be produced by various methods, for example:

A. by condensation of one mole of dicarbony compound of the Formula II

IX N. __ I ... Π / S.

-Υ '- <^ Β> - C = 0 (II) n-1

with 2 moles of the same or different malonic acid derivatives Formula III andΊIIa

ν- γ

/ ^X l ^ ^X l.

CH ₂ (HI) ₅ CU, (HIa)

\ X ₂ \ X ₂ ¹

under the known conditions of condensation according to Knoevenagel.

In some cases, especially when Rc or Rc ¹ are different from hydrogen, the reactivity of the dicarbony compounds of Formula II is not sufficient for a successful condensation. An improvement is achieved in such cases when the carbonyl compounds are converted into activated forms, such as the corresponding bis-dichlorides or bis-imines, before the reaction with the malonic acid derivatives, e.g. with cyclohexylamine into the corresponding double Schiff base.

B. by reaction - of 2 mol · same or different Compounds of the formulas IV and IVa

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■ ι ⁵ Λ - 12 - Y ^,! ~ < R '
I ⁵ 1
Λ 568693
» ι Υ _Ί - - C = σ (IV); χ - O = C. (IVa) 1 ^ΝΧ 2

where Y, or Y, ^{1 is} the hydroxyl or amino group, with one mole of a functional alkylation or acylation

by means of the formula V.

ZR ₆ -Z (V)

in which Z for Y, or Y, '= HO -, halogen, preferably chlorine, bromine or iodine, or the remainder of a strong oxygen acid, preferably the remainder of a sulfur-oxo acid, for example the remainder -OSO ₃ , -0S0 ₂ -lower-alkyl or -OSO ₂ -aryl or for Y ₁ or Y ₁ ¹ = NH ₂ -, the group -COZ ', -SO ₂ Z ¹ or -OCOZ', with the meaning of halogen, preferably Means chlorine for Z ^1. Suitable alkylating agents of the formula V are thus bisesters of diols of the formula HO-Rg-OH, which are derived from hydrohalic acid or a strong oxygen acid. Suitable acylating agents are therefore dicarboxylic acid halides; the dicarboxylic acid chlorides are particularly suitable and easily accessible. Method B can naturally only be used for the synthesis of compounds in which n = 2 .

The dicarbonyl compounds required for method A. Formula II are partly known and are either according to the usual Aldehyde or ketone syntheses or, if n = 2, also by etherification

or acylation of 1 mole each of the corresponding carbonyl compounds of formula VI and VI a

(VI) j Y ₁ ^% - <£ B ^N VC = 0 (VIa)

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by the bifunctional alkylation or. Aeylating agent der Formula V received. ■

These carbonyl compounds of the formula VI or VIa can of course also first be mixed with the malonic acid derivatives of the formula III or IHa, as described above for method A, to the methylenemalonic acid derivatives of formula IV or »IVa are condensed, which are then further reacted according to method B.

Examples of the starting products in the processes described above and to illustrate the various symbols X, Y, R and Z are:
1. Malonic acid derivatives of the formula III or HIa, illustrative of X:

Malonic acid dimethyl, diethyl, dipropyl, dibutyl - ^ - dioctyl, -didodecyl *, -dioctadecyl-, -di-2-ethylhexyl-, -diallyl-, -dioleyl-,

-di-m-butoxybenzyl-,

-dibenzyl, -di-2-phenylethyl-, -di-p-methoxybenzyl-, / - di-o-methylbenzyl-, -di-p-dodecylbenzyl-, -di-cyclopentyl-, -di-cyclohexyl-, -di-3-methylcyclohexyl-, -di-4 *, butyl cyclohexyl-, -di-2-methoxyethyl-, -di-2- (2-butoxyethoxy) -ethyl-, -di-2-dodecyloxyethyl, -di-2-benzyloxyethyl-, -di-2-phenoxy-propyl-ester, malonic acid bisdimethyl-, -bis-diethyl-, -bismethylethyl-, -bismethyl-3-methoxypropyl-amide, Malonic acid bismorpholide and malonic acid bispiperidide / cyanoacetic acid methyl ester, Decyl cyanoacetate, ■ Octadecyl cyanoacetate, 2-methoxyethyl cyanoacetate, Benzyl cyanoacetate, cyanoacetic acid morpholide, cyanoacetic acid dibutylamide and malodonitrile »

2a. . Bifunctional alkylating agents of the formula V, illustrative of the symbols R _g and Z: 1,2-dibromoethane, 1-bromine ».3-chloropropane,

_ο 1,4-dichlorobutane, 1,8-dibromooctane _? 1,12-dibromododecane, propane

• to ... ¹ 1,3-dimethanesulfonate, butane-l ^ -bis-benEolsulfoiiat, pentane-1,5-co
- * 'b'is-sulfuric acid ester, l, 7-dichloro-4-thiaheptane, l, 7-diiodo-4-2t "■ oxaheptane * S-oxanonane-l ^ -di-benzenesulfonate, 3,6-di-OXa - and / ^

to -Di-thia-octane-lje-dl-p-toluenesulfonate, ice »and trans-1,4-. O °

Bis-chloromethylcyclohexane, 2,2,4,4-tetramethyl-cyclobutane-1,3-bis-p-toluenesulfonate, Cyclodecane-1,6-di-p-chlorobenzenesulfonate, p-Chloromethylbenzyl chloride, bis-methanesulfenic acid ester of p-bis- (3-hydroxybutyl) -benzene (The diol is obtained from p-Bis-fS-oxo-buten-CD-ylJ-benzene, which can be obtained from acetone and terephthalaldehyde obtained), 4- (2-chloroethoxy) - benzyl chloride (by chloromethylation obtained from l-phenoxy-2-chloroethane), p-bis (4,4-dioxo-3-oxa-4-thiapentyloxy) benzene (obtained by esterifying p-bis (2-hydroxyethoxy) benzene with methanesulfonic acid chloride).

2 B. Bifunctional acylating agents of the formula V: oxalyl chloride, Adipic acid dichloride, sebacic acid dichloride, terephthalic acid dichloride, isophthalic acid dibromide, cyclohexane-l ^ -dicarboxylic acid chloride, Homoterephthalic acid dichloride, benzene-l, 3-disulphonic acid chloride, the dichloride of sulfoacetic acid, the dichloride of Phenylacetic acid-4-sulfonic acid, the dichloride of ethane-1,2-disulfonic acid or butane-1,4-disulfonic acid, also butane-1,4-diol-bischloroformate, Hexane-l ^ -diol-bisehloroformiate.

3. Carbonyl compounds of the formula VI or VIa, illustrative of ■ the symbols Y ₁ or Y ₁ ¹ , R ₅ or R ₅ ¹ and the substitution in the benzene rings A and B: p-hydroxybenzaldehyde, 3-chloro-4- Hydroxybenzaldehyde, 3-iso-propyl-4-hydroxybenzaldehyde, 2-methoxy- and 3-methoxy-4-hydroxybenzaldehyde, 3,5-dimethybenzaldehyde, 2-butoxy-4-hydroxybenzaldehyde (these aldehydes are produced using the Vilsmeier-Haack method obtained), p-aminobenzaldehyde, p-hydroxyacetophenone, p-hydroxybutyrophenone, 3-bromo-4-hydroxyacetophenone, 4-hydroxybenzophenone, 4-hydroxy-4'-methoxybenzophenone, 4-hydroxy-4-ethylbenzophenone, 3-methyl-4- hydroxy-4'-butoxybenzophenone (these. ketones are obtained by Friedel-Crafts acylation of the corresponding ·

Obtained phenols). - * ■

BATH ORIGINAL;

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"4. Dicarbonyl compounds of the formula II, illustrative of the symbols Y or Y ¹ , R ₅ or R ₅ ¹ , R ₆ , η and the substitution in the benzene rings A and B: 4.4 ^t -diformyldiphenyl ether, 3-chloro -4,4'-diformyldiphenyl ether (both obtained from the corresponding tetrabromo compounds by saponification or, according to Sommelet, from the chloromethyl compounds.), 1,4-bis- (4-formylphenoxy) -butane, 1,2-bis- (3 methyl-4-formylphenoxy) ethane (both obtained from Gattermann), 1,5-bis (4-acetylphenoxy) pentane (obtained by etherification of p-hydroxyacetophenone with 1,5-dibromobutane) 4,4 · diacety 144,4 · -Dipropionyl-, 4, -4'-dipivaldyl- and 4,4'-dibenzoyl-diphenyl ethers (obtained according to Friedel-Crafts). 5 * Monomethylene malonic acid derivatives of the formula IV or IVa:

α-carbethoxy-β- (p-hydroxyphenyl) acrylic acid diethylamide, α-carbethoxy-β- (4-hydroxy-2-chlorophenyl) acrylic acid piperidide. Of course, esters, in particular lower alkanol esters, of bismethylene malone derivatives, i.e. compounds of the formula I, can be used in where X is the group -COORp, where Rp is a lower alkyl radical, either by transesterification into other esters or by reaction with Amines are converted into amides. Example catfish can do that 1,4-bis- [4- (2,2-dicarbethoxyethyl) phenoxy] butane by means of overmestering with octadecyl alcohol into 1,4-bis [4- (2,2-dicarboocta-decyloxyethenyl) phenoxy] butane convict. In addition to the simple alkanols, oxaalkanols, such as 4-methoxybutanol, are also suitable for transesterification. 2-dodecyloxyethanol or 2- (2-butoxyethoxy) ethanol, or hydroxy alcohols, such as ethylene glycol, diethylene glycol, butane-1,4-diol or triethylene glycol.

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The new UV absorbers of the formula I are incorporated into the light-sensitive, in particular polymeric, carriers for light filters in amounts of $ 0.01 to $ 30. The amount of UV absorbers to be incorporated depends, among other things, on the thickness of the light filters to be produced. For very thin layers, as they are, for example, for paint coatings in question, amounts are from 1 to 20Ji preferably, for thick layers, however, amounts as plates, for example, polymethacrylate ¹ of 0.01 to 1% preferred.

The carrier materials for the new bismethylene malonic acid derivatives of the formula I are primarily organic polymers called} both thermoplastic polymers and curable synthetic resins (thermosetting polymers) are possible, namely both fully synthetic polymers and natural polymers, as well as their polymer-homologous chemical modification products. Under the fully synthetic polymers are mainly pure additives and pure condensation polymers, but also condensation polymers crosslinked by addition polymerization. the Addition polymers which can be used as carrier materials for the new light stabilizers can include the following Main types can be assigned:

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1 * homopolymers and copolymers of vinyl and vinylidene monomers, by radical, ionic or organometallic polymerization initiators be converted into the corresponding polymers. - Examples of such monomers, their polymers or copolymers, suitable as carrier materials are:

Polymerizable ethylenically unsaturated halogenated hydrocarbon compounds, especially vinyl chloride, vinyl fluoride and vinylidene chloride, polymerizable hydrocarbons with addition-capable double bond, especially styrene, isobutylene, ethylene and propylene, both the atactic and the isotactic polymer forms come into question.

α, β-unsaturated polymerizable carboxylic acids "and their functional derivatives, such as acrylic acid, methacrylic acid, acrylonitrile, alkyl esters (especially lower alkyl esters) and amides

acrylic and methacrylic acid, for example the methyl, ethyl and butyl esters of methacrylic acid and acrylic acid;

Polymerizable acyl derivatives of ethylenically unsaturated alcohols and amines, especially those organic carboxylic acids, acyl radicals of alkanoic and alkene carboxylic acids with up to 18 carbon atoms and from aromatic uionocyclic carboxylic acids such as • Benzoic acids and phthalic acids, as well as cyclic carbonic acid imides, such as those of cyanuric acid, for example. Examples are allyl phthalate, polyallyl melamine, vinyl acetate, vinyl stearate, Vinyl benzoate and vinyl maleate, polymerizable polyenes with conjugated double bonds, such as butadiene, isoprene, chloroprene,

Sorbic acid and its esters. _. - - - - ~ ~ *

009812/192 7 bad original.

2. Homopolymers and copolymers of epoxies, in particular of bisepoxides, caused by acid or base catalytic hardening. For example, the polymers come in this class Bisglycidyl ethers of the geminal bis (p-hydroxyphenyl) alkanes and cycloalkanes in question.

3. Homopolymers and copolymers of lactams and lactones, in particular the polymers of ε-caprolactam.

4. Homo- and copolymers of aldehydes, in particular of formaldehyde and acetaldehyde, such as polyoxymethylene and polyoxyethylene. ' ^f '

5. reaction products of isocyanates with hydroxyl and / or amino compounds, in particular those of di- or polyisocyanates with di- or polyvalent hydroxyl or amino compounds. In these Polyurethanes and polyureas come in class, which are produced by reacting diisocyanates with hydroxyl-containing polyesters and / or polyether arise.

The condensation polymers used as carrier materials for the new UV absorbers that come into consideration are, among others, in particular polyesters and polyamides. Thereby are particularly linear thermoplastic polycondensates, which are derived from dicarboxylic acids and organic dihydroxy derivatives or organic ' Derive diamines on the one hand and hydroxy or aminocarboxylic acids on the other hand. Preferred linear polycondensates are the fiber-forming ones Polymers of U3, o> s-dicarboxylic acids and ω, ωί-dihydroxy compounds or U ^ i-diamines, as well as of UJ-hydroxycarboxylic acids or of OJ-aminocarboxylic acids, especially those polymers that differ from saturated

009812/1927

aliphatic, cycloaliphatic]! and carbocyclic not Derive fused aromatic carboxylic acids.

The linear condensation products of the following components are particularly suitable: adipic acid-hexamethylenediamine, Sebacic acid-hexamethylenediamine, terephthalic acid-ethylene glycol, Terephthalic acid 1,4-dimethylol-cyclohexane, 10-aminodecanecarboxylic acid (11-aminoundecylic acid).

Crosslinked polycondensates as carrier materials are "thermosetting ^11" and arise in particular through the condensation of aldehydes with polyvalent condensable compounds. Mentioned selenium formaldehyde condensates with phenols, ureas and melamines.

Polyester resins in particular are among the condensation polymers crosslinked by subsequent addition polymerization i.e. copolymers of polyesters of unsaturated organic carboxylic acids which contain double bonds capable of addition, with polyhydric, especially dihydric alcohols, these polyesters optionally with non-addition-capable dicarboxylic acids modified are on the one hand, with vinyl or vinylidene monomers on the other hand. Polymerizable monomers are preferably used Mixtures of condensates of maleic acid, itaconic acid, citraconic acid with dihydric alcohols, preferably the Water addition products of ethylene and propylene oxide, such as Ethylene glycol, propylene glycol and diethylene glycol and optionally other dicarboxylic acids of the aliphatic, alicyclic and monocyclic-aromatic series or their anhydrides, such as Succinic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, of the anhydride of 1, 2, 3, 4, 7, 7-Hexychlordicyclo-

009812/1927. / '

" , BATH

[2,2, rJ-hept-2-en-5,6-dicarboxylic acid and / or adipic acid and from Styrene and / or methyl methacrylate in question. ',

This monomer mixture of unsaturated polyesters' and vinyl and / or vinylidene monomers (often referred to as liquid polyester resin) in a preferred embodiment radical polymerization initiators crosslinked.

The natural polymers that can be used as carrier materials for the new UV absorbers are mainly polysaccharides, such as cellulose, or rubber and proteins.

The reaction products of Polyvinyl alcohols with aldehydes, such as polyvinyl butyral, and the saponification products of polyvinyl esters should be mentioned. Polymer homolog Chemically modified natural polymers as carrier materials for the new light stabilizers are primarily the cellulose esters and ethers, such as the cellulose esters of acetic acid, propionic acid and benzoic acid, with an average of 1 to 3 acyl groups per glucose unit.

The ones given in the above list

Polymers are in compositions of matter obtained according to the invention for themselves or in mixtures, the carriers of the new light stabilizers. ' Contain particularly valuable material compositions as a carrier the new light stabilizers thermoplastic vinyl and vinylidene polymers including polyolefins, cellulose esters and ethers, linear fiber-forming polyesters, polyamides and polyurethanes, polyester resins. V

009812/1927

In addition to these polymeric carriers, there are natural and synthetic light-sensitive waxes, fats and oils, as well complex systems such as photographic material, emulsions containing light-sensitive fatty substances, emulsions or dispersions of the above-mentioned polymers as carrier materials for the new light stabilizers in question., As an example, consider a UV-absorbing Emulsion of a solution of the compounds of the formula I in high-boiling solvents, such as dioctyl phthalate, dioctyl sebacate, or mentioned in the gelatin layer of photographic materials. Pas molecular weight of the aforementioned polymers plays a subordinate role as long as it is within the range for the characteristic mechanical properties of the relevant Polymers necessary limit values. Depending on the polymer, it can range from 1,000 to several million the new UV absorber in these polymers is done, for example, depending on the type of polymer, by incorporating at least one these compounds and possibly other additives, such as plasticizers, antioxidants, other light protection agents, Heat stabilizers, pigments in the melt according to the methods customary in technology, before or during shaping, or by dissolving in the corresponding monomer before the polymerization or by dissolving the polymer and the additives in solvents and subsequent evaporation of the latter. The new bismethylene malonic acid derivatives can also be taken from bathrooms, for example. ' from aqueous dispersions to thinner support structures, such as on Films or threads.

The incorporation of the inventive

g «mass of light stabilizers in the monomer mixture of condensation polymers, during the condensation at temperatures t | fe®r__2Pp ° G

0 0 9 812/1927 ^BAD original

Splitting off water. The incorporation of the Sunscreens in approximately neutral · Carrier is most beneficial.

The light-sensitive materials can also be protected from the harmful effects of light in that they with a protective layer containing at least one defined compound of the formula I, for example with a Varnish, or that they are covered with structures containing light stabilizers, such as films, panes or plates. In these two cases, the amount of light stabilizers added is advantageously XO to $ 30 (based on the protective layer material) for protective layers less than 0.01 mm thick, and 1 to 10 ^ for protective layers from 0.01 to 0.1 mm thick.

With certain types of use, especially when warm polymers in the form of chips have to be powdered with protective substances, are UV absorbers that are above the softening temperature of the relevant Polymers melt, and are nevertheless sufficiently soluble in the molten polymer ^ particularly valuable.

Obviously, the preferred carriers for the new bismethylene malonic acid derivatives of the formula I are thermoplastic Plastics that are processed into structures with a large surface at elevated temperatures. These are especially the polyolefins, i.e. polyethylene and the isotactic polymers derived from α-olefins, in particular from alkenes with 3 to 6 carbon atoms, derive. In addition, there are carriers that are characterized by a particularly low inherent color, such as polymers of the esters of Acrylic and methacrylic acids and polystyrene of importance.

BATH

009812/1927

A third type of carrier in which the inventive Bismethylene malonic acid derivatives lead to particularly good results, are polymers used as additional stabilizers or as pigments Sehwermetal salts are incorporated. These are mainly polymer halovinyl and vinylidene compounds, plasticized or above all in the form of heat-resistant compositions, such as for example rigid PVC.

Because of their easy accessibility and substrate compatibility

are symmetrical compounds of the formula Ia,

0 0

II I!

R_ - σ c -

c = CH - <r voV -o - <y .Λ> - gh = σ

\ - = L / ⁶ XZ- / \ 3 - R ₁ '(Ia)

4 A 0 0

in the

R ₁ 'is an alkoxy group with 1 to 21 carbon atoms and Rg' is an alkylene group with 2 to 12 carbon atoms, compounds in which all R-, 'and Rg ¹ together are at least 12, preferably 20 to 86, but especially 20-48 Containing carbon atoms, are particularly suitable as light stabilizers for polyolefins, such as polyethylene, isotactic polypropylene and isotactic poly-4-methylpentene- (l). Among the compounds of the formula Ia, the esters are distinguished by better compatibility with the same number of carbon atoms. The amides are preferred in those areas of application in which particular extraction resistance is important. In this class, the high-melting compounds are often preferred, since they can be mixed better, especially with the powdery α-olefin polymers, than low-melting or even liquid additives

00 9 812/1927

7568693

and thus ensure a better homogeneity of the finished products.

The compounds of the formula Ia are characterized by high absorption in the short-wave range, while similar '' compounds of the formula I, in which R ₅ or R ^ ^{1 is} different from hydrogen, absorb less but at longer wavelengths. The good lightfastness of the compounds of the formula Ia is all the more surprising as the analogous cyano acid ester compounds in which one of the -COR, 'groups is replaced by the radical -CN, have very poor lightfastness.

Compounds of the formula (Ib) are particularly suitable for polyvinyl chloride:

"" "* CN

C =

wherein R ₁ ¹ and R ₆ ¹ are as defined in formula Ia and X 'represents a lower alkyl group.

Compounds of the formula (Ib) in which η = 1 are particularly advantageous. ·

With regard to lightfastness in oxidizing substrates, the compounds of the formula (Ic) are particularly suitable.

009812/1927

where R ·, ¹ and R _fi 'have the meaning given in formula Ia, R ₅ " ¹ for phenyl, methylphenyl, chlorophenyl and ·

Alkoxyphenyl and
. "X _1" stand for the group -COOR ₁ ¹ or -CN.

Draw the cyano group-containing compounds of the formula CIo) to those with -COOR, '- groups by a significant higher absorbance.

Of the other stabilizers to be used together with the light stabilizers according to the invention, if appropriate most important are the antioxidants and their synergists. The aniline and naphthylamine derivatives have a good effect, such as phenyl-a- and -ß-naphthylamine, Ν, Ν'-dibutyl-, -dioctyl-, -Diphenyl-p-phenylenediamine, 2,2,4-trimethyl-1,2-dihydroquinoline, 3-hydroxy-l, 2,3,4-tetrahydro-benzo [h] -quinoline, phenothiazine, N-butyl-p-aminophenol etc. All of these amino group containing antioxidants discolor in the air and are therefore only useful for deeply colored or black compositions. Far more important are however those that have little or no tendency to discolouration phenolic antioxidants. In substrates that have little tendency to auto-oxidize, such as polyvinyl chloride, are often sufficient already ginfache phenols, such as 2,2-bis- (4-hydroxyphenyl) -propane. In Substrates that are strongly subject to autoxidation, such as in α-polyolefins, which, in addition to polyethylene, especially the isotactic types that differ from alkenes with more than two carbon atoms derive, include, as in the homo- and co-polymers of butadiene and / or isoprene, sterically hindered phenols must be used as antioxidants. As examples of the simplest Representatives of this class are: 2,4-dimethyl-6-t.butyl-,

BATH

009812/1927

2,6-di-t-butyl-4-methyl-, 2-t-butyl-5-methyl- and 2,6-di-t-butyl-4-methoxyphenol. Mononuclear phenols substituted in the side chains, such as the alkanol esters of 2,6-di-t.butyl-4- (2-carboxyethyl) phenol, of 3,5-di-t.butyl-4, are less volatile and therefore preferred -hydroxybenzylphosphonic acid, 2,6-di-t-butyl-4-dimethylaminomethyl-phenol or phenols with complex hydrocarbon substituents, such as reaction products of phenol, p-cresol, m-cresol with terpenes. ^{Polynuclear phenolic antioxidants such as 4.4 l} -dihydroxy-2.2 ^l -dimethyl-5,5'-di-t.butyldiphenyl sulfide, 2, "2 * '-dihydroxy-3,3, are not very volatile and therefore suitable · -Di-t-butyl-5,5 »-dimethyldiphenylmethane, 4-methyl-, 4-ethyl-, 4-t-butyl-, 4-octyl-2,6-bis (2-hydroxy-3-t .butyl-5-methylbenzyl) -phenol, l, l-bis- (4-hydroxy-2-methyl-5-t-butylphenyl) -propane, l, l, 3-tris- (4-hydroxy-2-methyl -5-t-butylphenyl) -butane, 1,3,5-tris- (4-hydroxy-3,5-t-butylphenyl) -2,4,6-trimethylbenzene, 2,4,6-tris- (4th -hydroxy-3,5-t-butylphenyD-phenol, the triester of trimethylolpropane and the tetraester of pentaerythritol with 3 - (* l-hydroxy-3,5-di-t.butylphenyl) propanoic acid or the diester of ethylene glycol with 4-hydroxy-3,5-di-t.butylbenzoic acid, furthermore 2,4-dioctylmercapto-6- (4-hydroxy-3,5-di-t.butylphenylamino) -1,3,5-triazine, 2-octylmercapto -4,6- (4-hydroxy-3,5-di-t-butylphenoxy) -1, 3, '5-triazine, or 2r (2-octylmercapto-ethylmercapto) -4,6- (4-hydroxy-3 , 5-di-t-butylphenoxy) -1,3,5- triazine. In order to increase the effect of these actual antioxidants, especially if they are used in low concentrations, synergists can also be added to the compositions. The esters of thiodipropionic acid, in particular those of

009812/1927 ^BAD

higher fatty alcohols such as lauryl alcohol or octadecyl alcohol proven. The antioxidants mentioned are added to the plastic compositions containing light stabilizers in amounts of from 0.001 to 1 Part by weight and the synergists added in amounts of 0.01 to 2 parts by weight per 100 parts by weight of plastic.

To stabilize the color of plastics when exposed to heat, it is often advantageous to use phosphites such as triphenyl phosphite in addition to the light stabilizers Add amounts of 0.01 to 5 parts by weight per 100 parts by weight of plastic. This phosphite addition can of course continue be supplemented by the addition of antioxidants and / or synergists, if the substrate increases its sensitivity to heat and light is also subject to autoxidation.

The following examples illustrate the invention. The temperatures are given in degrees Celsius.

009812/192 7 ^ o OR ₁ QlNAt

example 1

A solution of 15 g of acetyl cellulose with an average of 2.5 acetoxy groups per glucose unit and 0.3 g of one in the • The additive listed in Table I below, 2.0 g of dibutyl phthalate and 82.7 g of acetone is spread onto a glass plate to form a film. The cellulose obtained after evaporation of the acetone

»Sea acetate foils are first dried at room temperature and then in the oven at 60 °. Samples of this 0.04 mm thick sheets are Ah fade-0-meter exposed and tested from time to time for their content of light stabilizers and their fragility. The received,

Results are shown in Table 1.

Table I.

Additive Conn.
No. Exposure
tion
duration
(Hours.) % noeh before
handenes
Additive behavior
the slide
when folding a 1,4-bis [4- (2,2-dicarbethoxy-
ethenyl) phenoxy] butane 1 24
100
500 100
99
90 foldable
foldable
foldable b 1,4-bis- [4- (2-cyano-2-carbetho-
xy-ethenyl) -phenoxy! -butane
(Comparison substance) A. 24
100
500 20th
6th
0 foldable
foldable
brittle C. none
* 24
100
500 - foldable
foldable
brittle

As can be seen from Table I, additive No. 1 of the formula is suitable

CH ₃ CH ₂ OOC

C = C

COOCH

H = C

009812/1927

ÖOOCH-OH,

BATH. OFUGINAL

as a light-resistant UV absorber, while the closely related one Comparative substance A is very sensitive to photolysis and is therefore unsuitable as a light stabilizer.

Manufacturing process A

For the production of the light protection agent no 0.1 mol (29.8 g) 1,4-bis (p-formylphenoxy) butane (3mp. 103 °; J. org. Chem. £ 6, 475 (1961)), 0.2 mol (32.0 g) of diethyl malonate, 0.5 g of benzoic acid, 2 g of piperidine and 100 ml Benzene heated to boiling on a water separator for 14 hours. About 3 ml of water will separate out. The cooled down The solution is filtered and the filtrate is evaporated. The honey-like residue crystallizes on rubbing. The thus obtained The crude product is recrystallized from methanol and then from ligroin. It melts at 102 - 103 ° and shows a Maximum of the UV absorption at approx. 317 nm.

The comparison substance A is analogous by reacting the bis-formyl compound mentioned with ethyl cyanoacetate obtain. It melts at 200 °.

In Table 1 a are further results with the invention Substances listed. All of the light protection agents listed are able to protect acetyl cellulose in such a way that the corresponding Films remain foldable even after 500 hours of exposure.

BAD ORiGIISiAL '

009812/1927

Table I a

Additive

Conn. No. Smp.

% additive still present after 500 h exposure

procedure

1,8-bis [4- (2,2-dicarbethoxyethhenyl) phenoxy] octane

1,2-bis- [4- (2,2-dicarbobutoxyethenyl) -phenoxyj-ethane

1,2-bis [4- (2,2-dicarbooctoxyethenyl) phenoxy / ethane

1,2-bis [4- (2,2-dicarbododecyloxyethyl) phenoxy / ethane

1,2-bis- [4- (2,2-dicarbomethoxyethenyl) phenoxy / ethane

1,8-bis- [4- (2,2-dicarbooctadecyloxyethenyl) -phenoxyj-octane

1,4-bis- [4- (2,2-dicarbethoxyethhenyl) -2-methoxyphenoxy-butane

1,4-bis [4- (2,2-dicarbethoxy- 'ethhenyl) -3-chlorophenoxy-butane

1,4-bis- [4- (2,2-dicarbooctadecyloxyethenyl) -3-methylphenoxyJ-butane

p-Bis - / [4- (2,2-dicarbethoxyethenyl) -phenoxyI-methylZ-benzene

1,4-bis- [4- (1-phenyl-2,2-dicarbethoxy-ethhenyl) -phenoxy-butane

10

11

12 103 °

64 °

■ 65 '

79-80 °

154 '

78 ⁽

111-112 °

105 °

69 °

151-152 °

141 °

85

78

70

70

85

23

46

80

90

009812/1927

m - 31 Additive - Conn.
No. M.p. 1568693 Ver
drive - η 1,4-bis [4- (l-phenyl-2,2-
dicarbooctoxy) -phenoxyj-butane 13th 70 ° % still
before- '
handenes
Additive
after 500 h
exposure D. ο 1,8-bis- [4- (l-phenyl-2,2-
dicarbethoxy-ethenyl) -
phenoxyJ-octane 14th 125 ° 98 C. P. Sebacic acid-bis- [4- (2,2-di-
carbomethoxy-ethenyl) -anilldj 15th 185 ° 88 E. q 1,4-bis- [4- (l-methyl-2-cyano-2-
carbomethoxy-ethhenyl) -phenoxy J-
butane 16 139 ° 60 F. Γ 1,4-bis- [4- (l-phenyl-2-cyano-2-
carbethoxy-ethenyl) -phenoxyj-
butane 17th 163 ° 78 G " S.
t p-bis - / "[4- (l-methyl-2-cyano-2-
carbomethoxy-ethhenyl) -phenoxy J-
methy χ] benzene 18th 157 ° 90 F. U ρ, ρ'-bis- (l-methyl-2-cyano-2-
carbomethoxy-ethenyl) -diphenyl-
oxide'
ρ, ρ -Bis- (l-methyl-2-cyano-2-
carbododecyloxy-ethenyl) -
diphenyloxide 19th
20th 142 °
58-60 ° 84 F.
F. ρ, p'-bis- (l-phenyl-2-cyano-2-
carbathoxy-ethenyl) -diphenyloxyd 21 140 ° 89
"90 G 87

009812/19 27

Compounds 2-7 are made according to the above Method A produced. ·

Manufacturing process B

Compounds 8-11 are obtained by method B. The synthesis of compound 9 is given as an example: _f

a) Preparation of 4- (2,2-dicarbethoxy-ethhenyl) -3-chlorophenol.

0.1 mol (15.7 g) 4-hydroxy-3-chlorobenzaldehyde,

0.1 mol (16.0 g) of diethyl malonate, 3 ml of piperidine, 0.8 g of benzoic acid and 200 ml of benzene are placed on a water separator for 10 hours heated to boiling. The benzene solution is evaporated to dryness. The residue melts, recrystallized from toluene, at 114 °.

b) Preparation of 1,4-bis [4- (2,2-dicarbethoxy-ethhenyl) -3-chlorophenoxy J-butane.

0.05 mol (14.7 g) of the compound prepared under a) are dissolved in the cold in 100 ml of dimethylformamide and added to this Solution add 0.05 moles (2.7 g) of dry sodium methylate and a spatula tip of sodium iodide. This solution is at 50-60 ° heated and within 5 minutes with 0.025 mol (5.4 g) 1,4-dibromobutane offset. The reaction mixture is then refluxed for 45 minutes. After cooling, the mixture is in 300 ml of water are poured, the resulting precipitate is filtered off with suction, washed with water and made from ethanol and then from Llgroin recrystallized. The compound 9 thus obtained melts at 105 °. * ··

0 0 9 812/1927 ^{BAD Of} »Oi _Nal

In the preparation of compound 11, instead of Dimethylformamide N-methylpyrrolidone used as solvent .

Manufacturing process G

Compounds 12 and 14 are made according to method C, which is given below for connection 12:

a.) Production of 1,4-bis [4- (phenyldichloromethyl) phenoxy] butane.

0.08 mole (36.0 g) 1,4-bis (4-benzoylphenoxy) butane heated to 150 ° for 30 minutes with 0.16 mol (33.3 g) of phosphorus pentachloride. Thereupon the formed phosphorus oxychloride is from The reaction mixture is distilled off in vacuo and the residue added with 200 ml of hot carbon tetrachloride, whereupon the 1,4-bis [4- (phenyldichloromethyl) phenoxy] butane in the cold crystallized out, which at 114-118 ° with decomposition melts.

b.) Production of 1,4-bis [4- (l-phenyl-2,2-dicarbethoxyethenyl) -phenoxyJ-butane.

2.5 g powdered and degreased with carbon tetrachloride Magnesium shavings are made with half of a mixture of

0.1 mol (16.0 g) of diethyl malonate and 17.5 ml of absolute Ethanol overlaid. The reaction is stopped by adding

BATH «*» ¹ *

009812/1927

0.5 ml of carbon tetrachloride . The reaction mixture starts to boil. The addition of the second half of the malonic ester-ethanol mixture is passed in such a way that the reaction is kept under gentle reflux. After the addition is complete, the reaction mixture is heated to boiling for 3 hours, then the excess alcohol is evaporated off in vacuo and the residue is mixed with a solution of 0.05 mol (28.0 g) of the compound prepared under a.) In 100 ml at 50 ° added dry xylene. After the exothermic reaction has subsided, the mixture is heated to 120 ° for a further 2 hours, then cooled and decomposed with 200 ml of 10% sulfuric acid. The xylene phase is separated off from the aqueous phase, washed neutral with water, dried over sodium sulfate and evaporated. 1,4-Bis- [4- (1-phenyl-2,2-dicarbethoxy-ethenyl) -phenoxyj-butane remains as a residue. It melts, recrystallized from ethanol and toluene, at 141 °.

Manufacturing process D

Compound 13 is obtained by transesterification of compound with n-octanol (method D).

0.01 mol (7.35 g) of the compound 12 is mixed with 0.05 mol (6.5 g) n-octanol and 0.1 g of sodium methylate in vacuo for 2 hours heated to 120 °. The hot reaction mixture is taken up with 100 ml of ligroin, filtered and the 'filtrate to dryness evaporated. The residue obtained is compound 13,

BAD OFUGiNAL

009812/1927

recrystallized twice from hexane, melts at 70 °. Manufacturing process E

Compound 15 is obtained by the following procedure E!

a) Production of sebacic acid bis (4-formyl anilide).

0.2 mole (24.2 g) p-aminobenzaldehyde (obtained from p-nitrotoluene according to Org.Synth. 31, '6 (1951)) are dissolved in 100 ml of pyridine. To this solution, 0.1 mol (23.9 g) sebacic acid dichloride was added dropwise, the reaction mixture was stirred at room temperature for 1 hour, heated to 80 ° for 5 minutes, cooled and treated with 200 ml of water. The precipitate formed is filtered off, washed with water and extracted from ethanol and recrystallized from glacial acetic acid. The sebacic acid bis (4-formyl-anilide) obtained in this way melts at 138-140 °.

b) Production of sebacic acid bis [4- (2,2-dicarbäthoxyäthenyi-anilidj :

0.025 mol (10.2 g) sebacic acid bis (4-formyl anilide) are with 0.05 mol (6.6 g) malonic acid dimethyl ester, 1 g piperidine and 0.2 g of benzoic acid in 100 ml of benzene for 12 hours on a water separator heated to boiling. The reaction solution is cooled, whereby seb'acic acid bis [4- (2,2-dicarbethoxy-ethhenyl) anilide] Crystallized in light yellow needles. These melt, after recrystallization from methyl ethyl ketone, at 185 °.

Manufacturing process F

* Connections 16, 18, 19 and 20 are

«V. ^K settlement of the corresponding ship ¹ see bases with the corresponding

to get speaking cyanoacetic acid esters, which method F *

* ° is given below for compound 19. * " _Q O

Preparation of p, p'-bis (1-methyl-2-cyano-2-carbomethoxyethenyl) -diphenyloxyd.

0.1 mol (25.4 g) ρ, ρ'-diacetyldiphenyloxide (m.p. 102 °; J. Prakt. Chem. [2] 1Γ7 »350 (1927)), 0.22 mol (21.8 g) Cyclohexylamine and 2 ml of glacial acetic acid are refluxed in 250 ml of benzene for 18 hours on a water separator. the Solution of the resulting ship see base is cooled and A mixture of 0.22 mol (21.8 g) of methyl cyanoacetate and 13.5 ml of glacial acetic acid was added within 1 hour. The reaction mixture is then heated to 60 ° for 2 hours, then cooled and the voluminous precipitate formed sucked off. The cyclohexylammonium acetate is washed out of the filter material with hot water and the insoluble one The residue was recrystallized from glacial acetic acid and from toluene. The compound 19 thus obtained melts at 142 °.

Compound 16 is prepared analogously from 1,4-bis- (4-acetyl-phenoxy) -butane.

Manufacturing process G

The connections 17 and 21 are via the corresponding Ketimines obtained by method G, which is illustrated for compound 21 may be.

a) Preparation of pjp'-bis-C-phenyliminomethyl) -diphenyloxyd.

A solution of 0.1 mole (48.8 g) p, p'-bis (phenyldi- ^ chloromethyl) -diphenyloxyd (produced according to the method Ca.) in 200 ml of dry chloroform is added dropwise at -50 ° to 500 ml of liquid ammonia. Then the reaction vessel is warmed up gradually to room temperature, stirring it until all the ammonia has evaporated. Then that becomes educated

0 0 9 8 12/1927

BAD OFUGiNAL

Ammonium chloride filtered off and the filtrate evaporated, where "· as residue ρ, ρ'-bis- (phenyliminomethyl) -diphenyloxyd obtained, which, recrystallized from benzene, melts at 138 °.

b) Production of ρ, ρ'-bis- (1-phenyl-2-cyano-2-carbethoxyethenyl ) -diphenyloxyd.

0.01 mol (3.8 g) of the compound obtained under a) and 0.02 mol (2.3 g) of ethyl cyanoacetate are dissolved in 100 ml absolute ethanol boiled under reflux for 12 hours. When the reaction solution cools, a honey-like mass is deposited, which crystallizes when rubbed with glacial acetic acid. The ρ, ρ'-bis (l-phenyl-2-cyano-2-carbethoxy-ethenyl) -diphenyloxyd obtained in this way after recrystallization once from toluene, it melts at 140 °.

BAD ORlGIMAL

0 0 9 812/1927

Example 2

Flammable liquid. Polyester resin is polymerized after the addition of 0.5 wt. % Of an additive of Table II with 1 wt. ^ Benzoyl peroxide at 80 ° to give 2.5 mm thick plates. The plates are post-cured at 120 °.

Plates produced and exposed in this way show a significantly lower degree of browning than equally exposed plates, but without the above called additives.

The polyester resin used was produced as follows: In a mixture of 170 g of ethylene glycol and 292 g of diethylene glycol a mixture of 343 g of maleic anhydride is added in portions at 80 ° and 428 g of tetrachlorophthalic anhydride entered. The temperature is increased after the air in the reaction vessel has been displaced by nitrogen within one hour to 150 °, then increased within 9 hours to 210 ° and then another hour at this temperature left. The mass is then cooled to 180 °, a vacuum is applied and the pressure is slowly reduced to 100 torr. These conditions are maintained until the acid number of the reaction mixture has fallen below 50.

100 g of the polyester thus obtained are mixed with 50 g of styrene mixed, and the mixture is made among those described above Conditions polymerized.

Similar results are obtained if the equivalent amount of phthalic anhydride is used instead of tetrachlorophthalic acid. However, the resulting polyester resin is then no sc hwe rbr ennbar ...

If the styrene is replaced by methyl methacrylate in the above procedure, sheets are obtained which in and of themselves have less tendency to brown and, moreover, are easier to stabilize. 009812/1927 ORIGINAL BATHROOM

Table II

Additive

Verbg.
No. Proceed 22nd B. 23 B. 24 A. 25th B. 26th ■ B 27 B. 2 B- 28 B. 29 B. 30th B.

1,4-bis [4- (2,2-dicarbooctadecyloxy-ethenyl) -phenoxy-butane 1,4-bis- [4- (2,2-dicarbotetradecyloxy-ethhenyl) -phenoxy-butane 1,4-bis- [4- (2,2-bis-morpholinocarbonyl-ethhenyl) -phenoxy-butane 1, A-BIs-fA- [2,2-dicarbo- (2-methoxyethoxy) -ethenyl-phenoxy / -butane 1,4-bis - / "4- [2,2-dicarbo- (2-hydroxyethoxy) -ethenyl J -phenoxy / -butane 1,4-bis- [4- (2,2-dicarbomethoxy-ethhenyl) -phenoxy J-butane

1,8-bis [4-C2,2-diearbethoxy-ethhenyl) -phenoxy] -octane

1,8-bis- [4- (2,2-dicarbethoxy-ethhenyl) -3-chlorophenoxyj-octane 1,8-bis- [4- (2,2-dicarbethoxy-ethhenyl) -3-methylphenoxy] -octane 1,8-bis- [4- (2,2-dicarbethoxy-ethhenyl) -3-methoxyphenoxyj-octane

Compound # 22 is prepared by Method B as follows: a) Production of the Malonsfiuredioctadecylesters.

0.54 MoK 56.9 g) calonic acid, 1.1 mol (297 g) stearyl alcohol and 500 ml of benzene are boiled for 20 hours on a water separator heated and then p-toluenesulfonic acid in portions every 2 hours,

009812/1927

8AD

a total of 15 g was added. 20 ml of water are separated out. The benzene solution obtained is cooled with ice and the separated ester is filtered off with suction. Recrystallization from acetone gives 77 % of theory of pure dioctadecyl malonate (melting point 60 °).

b) Production of p- (2,2-dicarbooctadecyloxy-ethenyl) -phenol ..

0.2 mole (24.5 g of ^ p-hydroxybenzaldehyde, 0.2 mole (121.5 g) dioctadecyl malonate, 5 ml piperidine, 1 g benzoic acid and 300 ml benzene are placed on the water separator for 12 hours heated to boiling. 8.5 ml of water are thereby separated out. The benzene solution obtained is concentrated in vacuo. The residue is recrystallized from acetone and then melts at 69 °.

c) Preparation of the 1,4-bis [4- (2,2-dicarbooctadecyloxy-ethj £ uci) -phenoxy-butane.

To 100 ml of cold dimethylformamide are successively 0.06 mol (42.7 g) of the above phenol, 0.06 mol (3.24 g) of dry Add sodium methylate and a spatula tip of sodium iodide. The mixture is heated to 50-60 ° and within 5 minutes with 0.03 mol (6.5 g) of dibromobutane were added. After the addition is complete, the reaction mixture is refluxed for 45 minutes, then cooled with ice and acetone added dropwise with stirring until the initially amorphous precipitate crystallizes. The crude 1,4-bis [4- (2,2-dicarbooctadecyloxy-ethenyl) -phenoxyJ-butane is suction filtered and recrystallized from methyl ethyl ketone.

ι are so 19 g slightly out of focus at 82 ° melting pure product

obtain.

009812/1927

The compounds Nos. 23-27 are analogous to the Method B obtained, with the corresponding malonic acid

. derivatives is assumed. In the production of the malonic acid di (ß-hydroxyethyl) ester recommends seeing a big one

. Use excess ethylene glycol.

Compound no.2 is produced according to method B as follows:

a) 0.5 mol (61 g) p-hydroxybenzaldehyde, 0.5 mol (80 g) Malonic acid diethyl ester, 4 ml of piperidine and 1 g of benzoic acid heated to boiling in 500 ml of benzene for 14 hours on a water separator. 8.6 ml of water separate out. The benzene solution obtained is evaporated after filtering. The residue is solidified by trituration with a little ethanol. The recrystallized from ethanol p-Hydroxybenzylidenmalonsäurediethylester melts at 93 ° and is won with a yield of about $ 56,

b) To an ethylate solution prepared from 2.3 g of sodium metal and 200 ml of ethanol are successively in the cold 0.1 mol (26.4 g) p-hydroxybenzylidenemalonic acid diethyl ester, 0.1 mole (27.2 g) 1,8-dibromooctane and a spatula tip of potassium iodide given. The orange-red solution obtained is refluxed for 14 hours, its hue slowly changing to yellow-orange changes. By chasing off the ethanol and rubbing the residue, a crystalline mass is obtained from which by Wash with water and recrystallize from ethanol

-o ¹⁰² " ¹⁰³ ° ^{melting 1,8} -bis [4- (2,2-dicarbethoxy-ethenyl) -O ₀ phenoxyj-octane is obtained. It shows a strong melting point depression with the coincidentally same high melting point

"■ * Tie No. 1 of Example 1.

• ^ . . Compounds nos. 28-30 are prepared by method B like compound nos. 2. Instead of the p-hydroxy-benzal

BATH

dehydes becomes an equivalent amount of 4-hydroxy-3-chlorobenzaldehyde, 4-hydroxy-3-methyl-benzaldehyde or 4-hydroxy-3-methoxybenzaldehyde used. Compound # 24 is prepared by Method A. It crystallizes with 1 1/2 moles of water of crystallization and starts to melt at approx. 85 °.

009812/1927

Example 3

100 parts of methyl methacrylate, 0.5 part of an additive from Table III and 0.2 part of lauroyl peroxide are mixed and polymerized at a temperature of 50-70 ° in sheet molds 2 mm thick.

As can be seen from the table below, such plates can be used as colorless UV filters.

Table III

ί Additive Conn.
No. #Trans
from Lj
waves
340 nm mission
dear
length
430 nm Ver
travel a p-bis - / "f 4- (2,2-dicarbaethoxy-aethenyl) -
phenoxy J-methyV-benzene 11 <1 92 B. b 1,4-bis _/ f [4- (2,2-dicarbethoxy-aethenyl) -
phenoxyJ-methyl7-cyclohexane
(Mixture of ice and trans) 31 <L 92 B. c 1,4-bis [4- (2,2-dicarbethoxy-ethhenyl) -
phenoxy] butane 1 <1 92 A. d
ϊ l, 12-bis [4- (2,2-dicarbethoxy-ethenyl) -
phdnoxyj-dodecane 32 <1 92 B. e 1,8-bis [4- (2,2-dicarbethoxyethenyl) -
phenoxy] -3,6-dithiaoctane 33 <1 92 B. none 86 92

009812/1927

BAD OFUGIN & L

Compound No. 11 is made by Method B as follows manufactured:

A solution of 0.02 mol (5.28 g) diethyl p-hydroxybenzylidenemalonate (prepared according to Example 2 a), 0.02 mol (1.08 g) sodium methylate and 0.01 mol (2.6 g) p-xylidenedibromide in 70 ml of N-methylpyrolidone is one hour heated to 130 °, the initially red color changing to light yellow. After cooling the reaction mixture with ice under the pale yellow crystals of the crude p-bis- / "[4- (2,2-dicarbethoxy-ethhenyl) -phenoxy] -methyl / - -benzene suction filtered, washed with water and recrystallized from ethanol and then toluene. The colorless ones thus obtained Crystals melt at 151 - 152 °.

Compounds Nos. 31-33 are obtained analogously if, instead of p-xylidenedibromide, an equivalent amount of the mixture of the cis-trans isomers of 1,4-dibromomethylcyclohexane (obtained from the corresponding alcohol with HBr), of 1,12-dibromododecane or the S ^
toluenesulfonates is used.

009812/1927

. Example 4

A mixture of 600 g of powdery emulsion polyvinyl chloride (K value 72, bulk density 0.43) 330 g of dloetyl phthalate and 10 g of an additive of Table IV 150 ° processed into foils.

When exposing films produced in this way, brown spots appear only after a period of 1.5 to 2 times longer than with similar films made without the addition of substances from Table IV.

Similar results are obtained when using polyvinyl chloride with a K value of 74 and a bulk density of 0.46 is used.

Addition of 10 g of barium cadmium laurate to that in the first section The mixture mentioned in this example produces films which are stabilized against the effects of both heat and light.

Table IV

Additive

Connection no.

procedure

1,4-bis- [4- (2,2-bis-ethylaminocarbonylä theny1) -phenoxyj-butane

ρ, ρ · -Bis- (2,2-dicarbethoxyethhenyl) -diphenyloxyd

1,2-bis- [4- (2,2-dicarbobenzyloxy-ethhenyl) -phenoxy-ethane

1,2-bis- / 4- [2,2-dicarbo- (2-benzyloxyethoxy) ethenyl-phenoxy / ethane

1,4-bis [4- (2,2-dicarbomethoxy-ethhenyl) -phenoxy J-but an 0 0 9812/1927

34 35 36

37 38

A A

BATH ORIGINAL

Additive link
No. Ver
travel f 1,2-bis [4- (2,2-dicarbethoxy-ethhenyl) -
phenoxyJ-ethane 39 A. G
H p, p ^f -Bis- (l-methyl-2-cyano-2-carbomethoxy-
ethenyl) -diphenyloxyd
p, p ^l -Bis- (l-methyl-2-cyano-2-carbooctadecyl-
oxyäthenyl) -diphenyloxyd 19th
40 F.
F. i ρ, ρ'-bis (ln-nonyl-2-cyano-2-carboethoxy-
ethenyl) -diphenyloxyd 41 F. J 1,4-bis [4- (l-methyl-2-cyano-2-carbomethoxy-
ethenyl) -phenoxyJ-butane 16 F.

For the production of the light protection agent No. 34 according to Method A is 0.1 mole (29.8 g) 1,4-bis-p-formylphenoxybutane, 0.2 mol (31.6 g) of malonic acid-bis-ethylamide, 0.5 g of benzoic acid, 2 g of piperidine and 200 ml of benzene for 14 hours on Water separator heated to boiling. (The malonic acid bisethylamide is made by reacting malonic acid ethyl ester with Obtained ethylamine; it melts at 148 °). The 1,4-bis [4- (2,2-bisr-ethylaminocarbonyl-ethenyl) -phenoxyJ-butane is obtained from the cooled solution suction filtered and recrystallized from chlorobenzene. It melts at 214 °.

The connections nos. 35 - 39 are on corresponding Kind of received by instead of used 1,4-bis-p-formylphenoxybutane, equimolar amounts ρ, ρ'-bisformyl-diphenyl ether (F: 55 °, CA 5.2 11465e) or

009812/1927

BATH OFUGIMAL

1,2-bis-p-formylphenoxyethane (F: 123 °; J. org. Chem. £ 6., 475 (1961)) can be reacted in an analogous manner with the corresponding amounts of malonic acid esters.

The connections 40 and 41 are according to the method F. obtain.

BAD ORlGIWAL

009812/1927

Example 5

Polyethylene having an average molecular weight 28 ¹ OOO and a density of 0.917 is in a Brabender plastograph with 1% of its total weight of an additive and 0.5 of Table V $ 4- (2-CarbooctadecyloxyäthyD ^ jo-di-t.butylphenol at 180 ° The mass thus obtained is pressed in a plate press at 165 ° to give 1 mm thick plates.

When exposed to weathering, these panels show a significantly lower tendency to become brittle than those without the addition of named additives.

Similar results are obtained when polypropylene is used instead of polyethylene; however, it must then be mixed at 220 ° and pressed at 180 °. If, instead of 4- (2-carbooctadecyloxyethyl) -2,6-di-t.butylphenol, 0.5 % of 4-hydroxy-3,5-di-t.butylbenzyl-di-t.octadecylphosphonate is used, at otherwise the same working method as indicated, similar results.

Table V

Additive
* link
No. Ver
travel a 1,4-bis- [4- (2,2-dicarbotetradecyloxy-
ethenyl) -phenoxyJ-butane 23 B. b 1,4-bis- [4- (2,2-dicarbooctadecyloxy-
ethenyl) -phenoxyJ-butane 22nd B. C. 1,6-bis- [4- (2,2-dicarbooctadecyloxy-
ethenyl) phenoxy (j -hexane) _{0 0 9 8} -, ₂ / -, ₉₂₇ 42 β;
ΐ
i

BAD ORJGINAL

Compound No. 23 is made by Method B as follows manufactured:

To 0.1 "mol (60 g) p- (2,2-dicarbotetradecyloxy-ethhenyl} -phenol (prepared analogously to Example 2b, F: 49-50 °) in 200 ml of dimethyl sulfoxide, 0.1. Mole (5.4 g) sodium methylate and a spatula tip of potassium iodide and the resulting solution at 50 ° within one hour 0.05 mol 10.8 g Dibromobutane was added dropwise. After stirring for 8 hours at 40, the dimethyl sulfoxide is evaporated in vacuo. The residue is taken up in acetone, the solution of the precipitated sodium bromide is filtered hot, the filtrate is cooled and the precipitated 1,4-bis- [4- (2,2-dicarbotetradecyloxy-ethenyd-phenoxyJ-butane recrystallized from hexane. It melts at 80 °.

Compound no. 42 is obtained if instead of p- (2,2-dicarbotetradecyloxy-ethhenyl) -phenol 0.1 mol (72 g) of the p- (2,2-Dicarbooctadecyloxyäthenyl) phenol described under 2 b with 0.05 mol (12.2 g) of 1,6-dibromohexane in analogous type is condensed.

_6A 0 009812/1927

Example 6

Polypropylene having an average molecular weight is 60 ¹ OOO and a density of 0.96 in the Brabender plastograph with 1% of its total weight of an additive of Table VI, 0.2% bis (4-hydroxy-2-methyl-5-t-butyl ) phenyl sulfide, 0.2 % dilaurylthiodipropionic acid and 0.2 $ tri-octadecyl phosphite mixed at 220 °. The mass obtained in this way is pressed in a plate press at 180 ° to give 1 mm thick plates.

The panels obtained in this way show a significantly lower tendency to become brittle than such when exposed to weathering without the addition of the additive mentioned in Table VI.

Similar results are obtained if, instead of the bis (4-hydroxy-2-methyl-5-t-butyl-phenyl) sulfide, 1,1,3-tris- (4-hydroxy-5-t-butyl-2- methyl-phenyl) -butane is used.

Table VI

Additive link
No. Ver
travel a
b
C. 1,2-bis- [4- (2,2-dicarbooctadecyloxy-
ethenyl) -phenoxyj-ethane
p-bis - / "[4- (2,2-dicarbooctadecyloxy-
ethenyl) -phenoxyj-methyl7-benzene
1,8-bis- [4- (2,2-dicarbohexadecyloxy-
ethenyl) -phenoxyJ-3,6-dithiaoctane 43
44
45 B.
B.
B.

009812/1927

The preparation of the compound no. 43 is carried out according to method B by condensation of 0.02 mol (14.3 g) of the phenol prepared according to Example 2b with 0.01 mol (1.9 g) of ethylene bromide in 30 ml of dimethylformamide and in the presence of 1.1 g of sodium methylate and a spatula tip Sodium iodide. The solvent is then used in a vacuum Evaporated to dryness and the residue recrystallized twice from hexane. The melting point of compound No. 43 is 73 °.

009812/1927

Example 7

Polystyrene granulate is mixed dry with 0.2 % of a light stabilizer from Table VII and 0.1 % tri-t.butylphenol and then injected using the automatic injection molding machine to form sheets 2 mm thick.

After exposure of the plates in the fade-0-meter during. For 2000 hours, the plates with a content of these light stabilizers in Table VII show practically no yellowing and no embrittlement, however, the samples are unprotected distinctly yellow and brittle. «

Similar results are obtained if 0.1% 2,6-di-t-butyl-4- (carbooctadecyloxyethyl) phenol is used instead of 0.1% tri-t.butylphenol.

ι Table VII

Additive link
No. a
b
*
C.
d 1,4-bis [4- (2,2-diearbethoxyethenyl) -
phenoxyJ-butane
1,2-bis [4- (2,2-dicarbethoxy-ethhenyl) -
phenoxy J-ethane
p-bis- / T4- (2,2-dicarbethoxy-ethenyl) -
phenoxyJ-methyl / benzene
1,8-bis ~ [4- (2,2-dicarbethoxy-ethenyl) -
phenoxy] octane 1
39
11
2

009812/1927

Example 8

Bleached maple veneer is coated with a wood varnish of the following composition:

15.0 parts by weight of cellulose acetate CELLIT F 900 from Bayer in Leverkusen, Germany, with about $ 56 acetic acid content,

10.0 parts by weight of dimethyl glycol phthalate,

2.25 parts by weight of compound no. 11, p-bis - / * [4- (2,2-dicarbäthoxyäthenyl) -phenoxy] -methyl / -benzene, (corresponding to 15% by weight based on cellulose acetate),

5.0 parts by weight of methyl alcohol, 10.0 parts by weight of toluene and 50.0 parts by weight of ethyl acetate. The natural yellowing of the wood is suppressed by this lacquer.

009812/1927

Example 9

Bleached maple veneer is finished with a wood varnish coated with the following composition:

16.0 parts by weight ACRONAL 4 F (BASF),

16.0 parts by weight of nitrocellulose E 620, $ 35 butanol moist (medium viscosity),

2.25 parts by weight of compound no. 21, p, p'-bis (1-phenyl-2-cyano-2-carbethoxy-ethhenyl) -diphenyloxyd,

44.0 parts by weight of butyl acetate and 24.0 parts by weight of toluene.

The natural yellowing of the wood is suppressed by this lacquer.

Similar good results are obtained when using 1,2-bis [4- (1-phenyl-2-cyano-2-carbomethoxyethenyl) phenoxy / ethane (Compound 46) instead of Compound 21.

009812/1927

Claims (6)

- 55 claims or -CN, where R _{1 is} the group means in which the substituents R ₂ , Rg and R * "do not have any of the atomic sequences -0-CO-, -NCO-, -NCS-, -C = CO- and -C = CN-, and where R ₉ and R, an optionally substituted alkyl, alkenyl, cycloalkyl, aralkyl, monooxaaralkyl or aryl group _t R _{4 is} an alkylene, monooxaalkylene or monothiaalkylene group, Y and Y 'each have a divalent radical of the formula -NHCO-, -NHSO ₂ -, -NHCOO-, which is bonded to ring A or B with the nitrogen, or -0-, R ₅ and R ₅ ¹ each represent an optionally substituted aryl group, or, if all X are exclusively -C0R -.- groups, also hydrogen, or, if at least two of the X are cyano groups, also an optionally substituted alkyl or aralkyl group, 009812/192 7 ^'B ^ ORJGINAL Rg is an alkylene, mono- or dioxaalkylene, mono- or dithialalkylene, cycloalkylene, aralkylene or monooxaaralkylene group and, if Y or Y ^{1 is} a nitrogen-containing group, also the phenylene group, where 2 or more are or are present in Rg. heteroatoms bound to Rg separated by at least two carbon atoms each and bound to Rg, this oxygen atoms connecting the benzene rings A and B to ge . saturated carbon atoms are bonded by Rg, and η 2 or, if Y is oxygen, also 1 and the benzene rings
A and B by chemically inert and non-coloring substituents can be substituted,
for stabilizing light-sensitive organic material. 2. Use of compounds of the formula I in which X ,, X ₁ , Χ «and Xp are independently the group -COR ₁ , Y and Y are oxygen, R ₅ and Rc are hydrogen or an optionally substituted aryl group, Rg is an alkylene, mono - or dioxaalkylene, mono- or dithiaalkylene, cycloalkylene, mean aralkylene or monooxaaralkylene group ¹ , where 2 or more heteroatoms present in Rg or bonded to Rg are separated by at least two carbon atoms each and the two oxygen atoms connecting Rg with the benzene rings * A and 3 are bonded to saturated carbon atoms, and R ₁ , η and A and B have the meaning given in formula I. 009812/1927 3. Organic material, characterized by a Content of a compound of the formula I. 4. A method for improving the resistance of photosensitive organic material, characterized in that that a compound of the formula I is incorporated superficially or homogeneously into such material. 5. Process for the preparation of compounds of the formula I, characterized in that one mole of a dicarbonyl compound of formula II, .O = C (ii) n-l in which for Y, Y, R ₅ , R ₅ , R ₆ , n, A and B the details given in claim apply, optionally after conversion into their activated forms, with 2 mol of the same or different malonic acid derivatives of the formulas III and IHa X-, CH, ^L 2
(III) ^X 2 (purple) Il in which X- ,, X ₂ , X ₁ and X _{2 have} the meaning given in claim 1, condensed. BATH ORIGINAL 009812/1927 6. Modification of the process according to claim 5 for the preparation of compounds of the formula I in which η = 2, characterized in that 2 moles of the same or different compounds of the formulas IV and IVa, (IV) (IV a) where Y-, or Y-, 'denote the hydroxyl or amino group, I ι 1 and X-,, X ₂ , X,, Χ «, R ₅ , R _5, A and B have the meaning given in claim 1, with one mole of a bifunctional alkylating or acylating agent of the formula V ZR ₆ -Z (V) converts, in which Z, when Y-, or Y-, = HO-, halogen or the residue of a strong oxygen acid, and when Y ₁ or Y ₁ '= H ₂ N-, the group -COZ' , -S0 ₂ z 'or -OCOZ ¹ , wherein Z' is halogen, means. i- • - ORIGINAL INSPECTED 4P / KS / ke / wi
June 27, 1966 009812/1927